Mekanisme Substitusi

Senyawa Kompleks

Saprini Hamdiani, Ph.D

Jurusan Kimia Fakultas MIPA Universitas Mataram
Mekanisme reaksi pertukaran ligan
Reaksi Umum:
MLn + X MLn-1X + L

 Reaksi pertukaran ligan:

L5MX + Y  L5MY + X

 Mekanisme Assosiatif, Dissosiatif, dan Interchange

Mekanisme Assosiatif
 L5MX + Y  L5MXY (bil.koordinasi 7)
 L5MXY  L5MY + X

Mekanisme Dissosiatif
 L5MX  L5M + X (bil.koordinasi 5)
 L5M + Y  L5MY
Perubahan struktur yang terjadi
 ReaktanMadyaProduk

 Dissosiatif:
Oktahedraltetragonal piramid (TP) atau trigonal bipiramid
TBPoktahedral
 ReaktanMadyaProduk

 Assosiatif:
Oktahedralpentagonal bipiramid (PBP) oktahedral
Mekanisme interchange
 Kebanyakan reaksi berlangsung dengan proses intermediet (antara a dan
d)
 Tahap pembentukan dan pemutusan ikatan tidak sepenuhnya berurutan
 berlangsung pada waktu yang sama  Mekanisme interchange (I)
 Mekanisme Interchange :
◦ Ia (interchange assosiatif)
Keadaan transisi : X---L5M-Y
Pembentukan ikatan M-Y menyebabkan pemutusan ikatan M-X

• Id (interchange dissosiatif)
• X-L5M---Y
• Pemutusan ikatan M-X menyebabkan pembentukan ikatan MY
Faktor yang mempengaruhi laju reaksi
pertukaran ligan
Faktor yang berpengaruh dissosiatif assoasiatif

1. Atom pusat
Muatan (+) ↓ ↑
Ukuran ↑ ↑
2. Gugus masukan
Muatan (-) No effect ↑
Ukuran No effect ↓
3. Gugus tinggalan
Muatan (-) ↓ ↓
Ukuran (-) ↑ ↓
4. Ligan lain
Muatan (-) ↑ ↓
Ukuran ↑ ↓
Bagaimana mengidentifikasi
suatu reaksi subsitusi apakah
assosiatif, dissosiatif atau
interchange??
Contoh 1 : reaksi pertukaran metanol dalam kompleks
[M(CH3OH)6][ClO4], M2+ = Ni2+, Co2+,Fe2+ dan Mn2+
Metal ΔS±, J K-1. Mol -1 ΔV±, cm3mol-1
Ni(II) +33,5 +11,4 (307 K)
Co(II) +30,1 +8,9 (279 K)
Fe(II) +12,6 +0,4 (255 K)
Mn(II) -50,2 -5,0 (279 K)

 Apabila:
 ΔS± > 0 dan ΔV± > 0 maka mengikuti mekanisme
dissosiatif  Ni(II) dan Co(II)
 ΔS± <0 dan ΔV± < 0 makan mengikuti mekanisme
assosiatif  Mn(II)
 ΔV± ~0 maka mengikuti mekanisme interchange  Fe(II)
Efek Gugus Masukan dan Gugus Tinggalan
kf
 [Co(NH3)5X]2+ + H2O [Co(NH3)5(H2O)]3+ + X
kr
 Reaksi maju (k ) : aquasi  penggantian X
f
oleh H2O (reaksi dengan air)
 Reaksi mundur (kr) : anasi  penggantian H2O
oleh X (reaksi dengan anion)
Contoh 2 : Anation of [Cr(NH3)5(H2O)]3+ is thought to proceed by
an interchange mechanism. The table below present rate
constant and activation parameters for interchange of the
entering and leaving groups in the Cr coordination sphere at 50
oC
Entering ligand 104 k (s-1) ΔH‡ (kJ/mol) ΔS‡ (J/mol K)
NCS- 6,12 102 12
HC2O4- 6,2 112 39
C2O42- 6,2 104 33
H3PO4 1,45
H2PO4- 1,45
[Co(CN)6]3- 2,5 103 26
H2O (exchange) 13,7 97 0

 What do these data suggest about the

intimate mechanism of these reaction?
The effect of the leaving groups on ligand substitution
reactions of octahedral complexes; rate constant for the acid
hydrolysis of [Co(NH3)5X]2+

X- kf, s-1 (at 25 oC) X- kf, s-1 (at 25 oC)

NCS- 5,0 x10-10 Cl- 1,7 x 10-6
N3- 2,1 x10-8 Br- 6,3 x10-6
HC2O4- 2,2 x10-8 I- 8,3 x10-6
F- 8,6 x10-8 NO3- 2,7 x10-5
H2PO4- 2,6 x10-7 SO3F- 2,2 x 10-2
The effect of the entering groups on ligand
substitution reactions of octahedral complexes; rate
constant for the acid hydrolysis of [Co(NH3)5(H2O)]3+

X- kf, s-1 (at 25 oC) X- kf, s-1 (at 25 oC)

NCS- 1,3 x10-6 NO3- 2,3 x 10-6

H3PO4- 2,0 x10-6 Br- 2,5 x10-6

Cl- 2,1 x10-6

Note: For comparison the rate constant for H2O

exchange by this complex is 6,6x10-6 s-1 at 25 oC
Rate constant of some anation reactions of
[Cr(H2O)6]3+

X- kf, s-1 (at 25 oC) X- kf, s-1 (at 25 oC)

I- 8 x10-10 HSO4- 1,3 x 10-7
SCN- 4 x10-9 NO3- 7,3 x10-7
Br- 9 x10-9 NCS- 1,8 x10-6
Cl-
2,9 x10-8 SO42- 1,1 x10-5

 For comparison the rate constant for H2O

exchange by this complex is 2,5x10-6 s-1 at 25
oC
Reaksi substitusi ligan pada
kompleks square planar
1.The trans effect
Apabila ligan yang memiliki efek trans lebih besar dapat
menyebabkan /mengarahkan ligan lain pada posisi trans
terhadap ligan tersebut pengarah struktur trans

T a σ-donor:
OH-<NH3<Cl-<Br-<CN-,CO,
CH3<I-<SCN-<PR3<H-

T a π-acceptor :
Br-<I-<NCS-<NO2-<CN-<CO, C2H4
Example:
 Use the trans effect series to suggest synthetic routes to cis-
and trans [PtCl2(NH3)2] from [Pt(NH3)4]2+ and [Pt(Cl)4]2-
 Given the reactans triphenylphosphane (PPh3), NH3 on
[Pt(Cl)4]-, propose efficient routes to cis- and trans-[PtCl2(NH3)
(PPh3)]
2.Steric effect
 Steric crowding at the reaction center is usually assumed to
inhibit Assocaitive reactions (a)
 Bulky groups can block the approach of attacking

nucleophiles, but the reduction of coordination number

(dissociative reaction) can relieve the crowding in the
activated complex
 Example: the rate constans for the hydrolysis of cis-

[PtClL(PEt3)2] complexes
 L= pyridine 2-methylpyridine 2,6-dimethylpyridine
8x10-2 2x10-4 1x10-6 (k/s-1)
3.Stereochemistry effect
 Cis complex gives a cis product
 Trans complex give a trans product

4. Temperature and pressure

dependence